Influence of Pre-Treatment on Remediation of Nitrobenzene Contaminated Groundwater by Combined Oxidation-Reduction Techniques
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摘要: 为了探究氧化与还原预处理对氧化-还原联合技术修复硝基苯污染地下水的影响，选取2，4-DNT（2，4-二硝基甲苯）为研究对象，构建过硫酸盐/铁炭修复技术体系，分别设置2个试验槽，一个试验槽以过硫酸盐作为氧化预处理联合以铁炭作为还原后处理，另一个试验槽以铁炭作为还原预处理联合以过硫酸盐作为氧化后处理，对比研究构建的氧化-还原联合系统中不同氧化与还原预处理方式对2，4-DNT去除机制的影响.结果表明：①过硫酸盐氧化材料填充位置显著影响试验槽pH和ORP（氧化还原电位）的变化，在运行周期5 PV（PV为孔隙体积，1 PV时间约为4 h）内，pH可显著增至11左右，ORP值达到最高.②在运行周期5 PV内，氧化填充层S2O82-浓度和还原填充层Fe2+浓度均显著降低.③在运行周期5 PV内，随运行周期的增加，以过硫酸盐作为氧化预处理联合以铁炭作为还原后处理的协同技术体系对2，4-DNT的去除效果显著降低，以铁炭作为还原预处理联合以过硫酸盐作为氧化后处理的协同技术体系对2，4-DNT的去除率维持在100%.④通过液相-质谱联用技术，识别构建的氧化-还原联合技术体系内2，4-DNT降解的主要中间产物，同时结合铁炭微电解还原机制和过硫酸盐氧化机制提出了2，4-DNT协同处理机制及其可能的降解路径.研究显示，还原预处理更有利于氧化-还原联合技术对地下水中2，4-DNT的去除，可为有效处理硝基苯化合物污染地下水提供理论支撑.
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关键词:
- 氧化预处理 /
- 还原预处理 /
- 2, 4-二硝基甲苯 /
- 中间产物 /
- 降解机制
Abstract: In order to investigate the effects of the oxidation and reduction pre-treatment on the combined oxidation-reduction techniques in the remediation of nitrobenzene contaminated groundwater, 2, 4-dinitrotoluene (2, 4-DNT) was chosen as the target contaminant and the persulfate-iron-carbon remediation technology system was constructed. Specifically, a large experimental trough of persulfate as oxidation pre-treatment combined with subsequent reduction post-treatment of iron-carbon mixture material and iron-carbon mixture material as reduction pre-treatment combined with subsequent oxidation post-treatment treatment of persulfate were set up. The effects of oxidation and reduction pre-treatment on 2, 4-DNT removal mechanism in the combined oxidation-reduction system were compared and studied. The results showed the filling position of persulfate material significantly affected the changes of pH and oxidation-reduction potential (ORP) in the large experimental trough. The pH could be significantly increased to about 11, and the ORP value reached the highest in the 5 pore volume (PV). Within 5 PV, the concentration of persulfate in the oxidized packed layer and the concentration of Fe2+ in the reduced packed layer decreased significantly. Within 5 PV, the removal efficiency of 2, 4-DNT in the large experimental trough of persulfate as oxidation pre-treatment combined with subsequent reduction post-treatment of iron-carbon mixture material was significantly reduced, whereas that in the large experimental trough of iron-carbon mixture material as reduction pre-treatment combined with subsequent oxidation post-treatment treatment of persulfate was maintained at 100%. The main intermediates of 2, 4-DNT degradation in the combined oxidation-reduction techniques system were identified by liquid chromatograph mass spectrometer (LC-MS). In combination with the iron-carbon micro-electrolysis reduction mechanism and persulfate oxidation mechanism, the collaborative treatment mechanism and possible degradation paths were proposed. Our results showed that the experimental trough of iron-carbon mixture material as reduction pre-treatment combined with subsequent oxidation post-treatment treatment of persulfate was more beneficial to the 2, 4-DNT removal in the combined oxidation-reduction remediation system, which provided theoretical support for the effective treatment of nitrobenzene contaminated groundwater. -
图 1 试验槽示意图
注：1、2、3、4、5、6、7为试验槽取样点编号.箭头为水流方向.
Figure 1. Schematic diagram of experimental tanks
图 2 运行周期1 PV、2 PV、3 PV和5 PV时试验槽1#和试验槽2#中不同取样点处pH的变化
Figure 2. Changes of pH at each sampling point in 1# and 2# tanks during 1 PV, 2 PV, 3 PV and 5 PV
图 3 运行周期1 PV、2 PV、3 PV和5 PV时试验槽1#和试验槽2#不同取样点处ORP的变化
Figure 3. Changes of ORP at each sampling point in 1# and 2# tanks during 1 PV, 2 PV, 3 PV and 5 PV
图 4 运行周期1 PV、2 PV、3 PV和5 PV时试验槽1#和试验槽2#不同取样点处Fe2+浓度的变化
Figure 4. Changes of the Fe2+ concentration at each sampling point in 1# and 2# tanks during 1 PV, 2 PV, 3 PV and 5 PV
图 5 运行周期1 PV、2 PV、3 PV和5 PV时试验槽1#和试验槽2#不同取样点处S2O82-浓度的变化
Figure 5. Changes of the S2O82- concentration at each sampling point in 1# and 2# tanks during 1 PV, 2 PV, 3 PV and 5 PV
图 6 运行周期1 PV、2 PV、3 PV和5 PV时试验槽1#和试验槽2#不同取样点处2, 4-DNT去除率的变化
Figure 6. Changes of the 2, 4-DNT concentration at each sampling point in 1# and 2# tanks during 1 PV, 2 PV, 3 PV and 5 PV
图 7 试验槽1#在PRMs填充层和ZVI/GAC填充层的质谱图
Figure 7. Mass spectrometry in the PRMs layer and ZVI/GAC layer in 1# tank
图 8 试验槽2#在ZVI/GAC填充层和PRMs填充层的质谱图
Figure 8. Mass spectrometry in the ZVI/GAC layer and the PRMs layer in 2# tank
图 9 2, 4-DNT在试验槽1#和试验槽2#预处理中可能的降解路径
Figure 9. 2, 4-DNT possible degradation paths in the different pre-treatment processes in 1# and 2# tanks
表 1 试验槽相关参数
Table 1. List of related parameters of test tanks
试验槽 PRMs/kg ZVI/kg GAC/kg 孔隙度 孔隙体积/m3 流速/(m3/h) 1# 250.1 251.3 123.6 0.43 2.58 0.5 2# 252.2 252.6 122.5 0.45 2.60 0.5 
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